This is a repository copy of Beam-induced oxidation of mixed-valent Fe (oxyhydr)oxides (green rust) monitored by STEM-EELS. White Rose Research Online URL for this paper: http://eprints.whiterose.ac.uk/144746/ Version: Accepted Version Article: Freeman, HM orcid.org/0000-0001-8242-9561, Perez, JPH, Hondow, N orcid.org/0000-0001-9368-2538 et al. (2 more authors) (2019) Beam-induced oxidation of mixed-valent Fe (oxyhydr)oxides (green rust) monitored by STEM-EELS. Micron, 122. pp. 46-52. ISSN 0968-4328 https://doi.org/10.1016/j.micron.2019.02.002 © 2019 Elsevier Ltd. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (http://creativecommons.org/licenses/by-nc-nd/4.0/). Reuse This article is distributed under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs (CC BY-NC-ND) licence. This licence only allows you to download this work and share it with others as long as you credit the authors, but you can’t change the article in any way or use it commercially. More information and the full terms of the licence here: https://creativecommons.org/licenses/ Takedown If you consider content in White Rose Research Online to be in breach of UK law, please notify us by emailing [email protected] including the URL of the record and the reason for the withdrawal request. [email protected] https://eprints.whiterose.ac.uk/ 1 Beam-induced oxidation of mixed-valent Fe (oxyhydr)oxides (green rust) monitored by STEM- 2 EELS 3 H.M.Freeman1,2, J.P.H Perez1,3, N. Hondow2, L.G. Benning1,3,4, A.P. Brown2. 4 1 GFZ German Research Center for Geosciences, Telegrafenberg, 14473 Potsdam, Germany 5 2 School of Chemical and Process Engineering, University of Leeds, Leeds, LS2 9JT, United Kingdom 6 3 Department of Earth Sciences, Free University of Berlin, 12249 Berlin, Germany 7 4 School of Earth and Environment, University of Leeds, Leeds, LS2 9JT, United Kingdom 8 Abstract 9 Analytical transmission electron microscopy (TEM) is often used to investigate morphologies, crystal 10 structures, chemical compositions and oxidation states of highly reactive mixed-valent mineral 11 phases. Of prime interest, due to its potential role in toxic metal remediation, is green rust sulphate II III 12 (GRSO4) an Fe -Fe layered double hydroxide. In this study, we quantified the effects that TEM 13 analysis has on GRSO4 in order to ensure the measured material properties are a result of synthesis and 14 reaction kinetics, and not due to sample preparation and analysis technique. To do this, we compared 15 two sample preparation techniques (anoxic drop-cast with drying, and frozen-hydrated cryogenic) and 16 exposed samples to the electron beam for several minutes, acquiring fluence series between ca. 40 e- 17 Å-2 and 10,000 e-Å-2. TEM imaging and electron diffraction showed that the hexagonal plate-like 18 morphology and crystal structure of GRSO4 were largely unaffected by sample preparation and analysis 19 technique. However, quantitative analysis of a series of monochromated Fe L3,2-edge electron energy 20 loss spectra (EELS) showed that electron irradiation induces oxidation. We measured an Fe(II)/Fe(III) - -2 21 ratio of 1.94 (as expected for GRSO4) at 50 e Å . However, above this fluence, the ratio 22 logarithmically decreased and dropped to ca. 0.5 after 1000 e-Å-2. This trend was approximately the 23 same for both sample preparation techniques implying that it is the beam alone which causes valence 24 state changes, and not exposure to oxygen during transfer into the TEM or the vacuum of the TEM 25 column. Ultimately this work demonstrates that GR valence can be quantified by EELS provided that 26 the sample is not over exposed to electrons. This also opens the possibility of quantifying the effect 1 27 of redox-sensitive toxic metals (e.g., As, Cr, Se) on Fe oxidation state in GR phases (relevant to the 28 treatment of contaminated soils and water) with a higher spatial resolution than other techniques (e.g., 29 Mössbauer spectroscopy). 30 KEYWORDS: monochromated EELS; Fe oxidation; green rust; cryo-TEM; low dose TEM. 31 HIGHLIGHTS: 32 Energy-resolved STEM-EELS to quantify Fe oxidation states in green rust 33 Demonstration of electron beam induced in situ oxidation 34 Methodology for quantifying the redox interaction between green rust and toxic metals 35 1. Introduction 36 Green rust (GR) materials are redox-active, mixed-valent Fe(II)-Fe(III) layered double hydroxides 37 which exhibit high surfaces area and can intercalate inorganic or organic species into the plate-like 38 structure due to their anion exchange capacity (Goh et al., 2008; Newman and Jones, 1998; Usman et 39 al., 2018). GR phases can be easily engineered for a wide-range of applications such as catalysis, 40 electrochemistry, and environmental remediation (Bhave and Shejwalkar, 2018; Chen et al., 2018; 41 Huang et al., 2019; Zhang et al., 2018). In particular, they are promising reactants for ground water 42 remediation where they have been shown to remove toxic metal contaminants from water by adsorption 43 (Jönsson and Sherman, 2008; Mitsunobu et al., 2009; Perez et al., 2019), reduction (O’Loughlin et al., 44 2003; Skovbjerg et al., 2006; Thomas et al., 2018), interlayer intercalation (Refait et al., 2000) and 45 substitution of structural Fe (Ahmed et al., 2008; Refait et al., 1990). II III 46 Green rust sulphate ([NaFe 6Fe 3(OH)18(SO4)2∙12H2O] hereafter referred to as GRSO4) is composed of 47 positively charged brucite-like iron hydroxide layers that alternate with interlayers containing sulphate 48 and water molecules (following Christiansen et al.). The structural Fe(II)/Fe(III) ratio of 2 has been 49 determined by Mössbauer spectroscopy, chemical analysis, and X-ray diffraction (Christiansen et al., 50 2009; Génin et al., 1996; Hansen et al., 1994; Perez et al., 2019; Refait et al., 1999, 1990). When using 51 GR for groundwater remediation, it is important the mineral remains stable and does not transform to 52 other iron (oxyhydr)oxides, which can be less effective substrates for the sequestration of toxic metals. 2 53 For example, partial oxidation or transformation of GR phases to other iron (oxyhydr)oxides can lessen 54 its ability to reduce redox-sensitive metals (e.g. Cr, Se, U) or its adsorption uptake (e.g. As) (Jönsson 55 and Sherman, 2008; O’Loughlin et al., 2003; Perez et al., 201λ; Skovbjerg et al., 2006; Thomas et al., 56 2018). One way to check the stability of GR over time is to monitor the Fe(II)/Fe(III) ratio following 57 interaction with metals. As such, it is essential that applied characterisation techniques can 58 quantitatively evaluate any changes in oxidation state resulting from environmental reactions and are 59 not a result of the characterization technique itself. Analytical transmission electron microscopy (TEM) 60 provides information at high spatial resolution regarding the morphology, crystal structure, chemical 61 composition and oxidation state of a specimen. To date, many TEM studies of GR have used 62 conventional sample preparation techniques (drop-cast and dried) under anoxic conditions (Ahmed et 63 al., 2010; Bach et al., 2014; Géhin et al., 2002; Mann et al., 1989; Perez et al., 2019; Skovbjerg et al., 64 2006; Thomas et al., 2018). Such methods involve aqueous sample dilution, drop casting onto a TEM 65 grid and drying with alcohol in an anaerobic chamber to minimise the risk of oxidation. The dried grid 66 thus contains a well dispersed sample that is subsequently exposed to air for rapid transfer into the 67 TEM. Much of the literature regarding TEM of GR has so far assumed that both sample preparation 68 and the TEM environment do not significantly affect the specimen. In some studies (particularly 69 Johnson et al. (2015)) these factors are taken into account, such as the short term air exposure during 70 sample transfer to the TEM and electron beam induced “nanoscale restructuring”, where low dose 71 operating conditions were used (Johnson et al., 2015). Here, we further explore these factors in relation 72 to the stability of the oxidation state by measuring electron energy loss spectra (EELS) at the valence 73 sensitive Fe L3,2-edge following both conventional (anoxic drop-cast and dried) and cryogenic (cryo; 74 frozen hydrated suspension) sample preparation for a range of controlled electron fluences. 75 Minimising exposure of GR to oxygen prior to TEM analysis and to vacuum dehydration during TEM 76 analysis can be achieved by retaining the mineral in a thin layer of vitreous ice; the grid must be wetted, 77 blotted and plunge frozen into liquid ethane for cryo transfer into the TEM. This method results in the 78 GR plates being dispersed in a thin layer of electron transparent, vitreous ice. Cryo-TEM has been 79 successfully used to investigate the formation of magnetite (Fe3O4) from a ferrihydrite precursor, which 3 80 can often proceed via GR as a transient phase, a process that had previously only been quantified by 81 time resolved X-ray diffraction (Dey et al., 2015; Michel et al., 2010; Sumoondur et al., 2008). The 82 cryo-TEM sample preparation used by Dey et al. (2015) was required to capture and monitor the 83 morphological changes of the gel-like ferrihydrite precursor phase at various points during the 84 transformation reaction. 85 Assessing a specimen’s sensitivity to electron irradiation can be achieved by collecting an electron 86 fluence series whereby the same area is repeatedly analysed during exposure to the electron beam. 87 Knowledge of the beam current, size of the analysed area, and the time the specimen is exposed to the 88 beam allows for the number of electrons per unit area (i.e.